CN103214605B - Isotatic polypropylene of a kind of terminal hydroxy group functionalization and preparation method thereof - Google Patents
Isotatic polypropylene of a kind of terminal hydroxy group functionalization and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to isotatic polypropylene, aim to provide isotatic polypropylene of a kind of terminal hydroxy group functionalization and preparation method thereof.The method comprises: under the condition of anhydrous and oxygen-free, joins in Schlenk bottle, finally add 40mg Primary Catalysts TiCl using organic solvent, aluminum alkyls, silicane external electron donor and metal alkylide class chain-transfer agent as promotor
4/ MgCl
2, pass into propylene; By dioxygen oxidation dry for polymerisate, carry out cancellation with aqueous hydrochloric acid, make catalyst deactivation, after stirring 5min, leave standstill separatory with separating funnel, in removing, the clear liquid of middle level; Solvent in removing solid product, then use distilled water and the drying of organic solvent repetitive scrubbing final vacuum, obtain the isotatic polypropylene that one end is hydroxyl.Chain-transfer agent used in the present invention, without the need to special synthesis, can add together with Primary Catalysts, and can not reduce the polymerization activity of Primary Catalysts; Primary Catalysts is industrial conventional TiCl
4/ MgCl
2catalyzer is not metallocene, is easy to realize industrialization.
Description
Technical field
The present invention relates to isotatic polypropylene, particularly a kind of isotatic polypropylene and preparation method thereof of terminal hydroxy group functionalization.
Background technology
Polypropylene because its mechanical property is good, the good and cost performance high of thermal characteristics and stable chemical performance, electrical insulation capability has a wide range of applications in fields such as packaging, automobile, building and military affairs.Within 2010, Pp In The World demand reaches 53,570kt, and aggregated capacity reaches 60,980kt/a, and the demand in the PP whole world and production capacity kept growth faster all always over the past two years.But polypropylene is unreactiveness, the nonpolar and crystalline feature of its molecular chain, determines its low surface energy and hydrophobic characteristic.Extremely low surface energy causes polypropylene interface compatibility when preparing matrix material with other organic and inorganic material is blended very poor, and the mechanical property of matrix material is greatly affected; Polyacrylic hydrophobicity also limit its application in dyeing, bonding, printing etc.Polypropylene is divided into isotatic polypropylene, syndiotactic polypropylene and Atactic Polypropelene, and wherein the consumption of isotatic polypropylene is maximum, and therefore the functionalization of isotatic polypropylene is the focus of scientific research always.
Polyacrylic functionalization mainly contains four kinds of methods: 1) surface treatment: be put into by isotatic polypropylene in the atmosphere of air, ozone, ammonia, with energetic ray, electron beam or plasma radiation, polyacrylic surface is processed, make its Surface Creation hydroxyl, carboxyl isopolarity group.This method needs expensive equipment, and modified effect can disappear with the prolongation of duration of service; 2) free radical grafting modification: mixed with maleic anhydride, vinylformic acid or acrylamide isopolarity monomer by polypropylene, causes polar monomer with radical initiator and carries out graft copolymerization, thus generates side base or the side chain of polarity.But easily there is degraded or crosslinked in polypropylene, greatly destroy the intrinsic mechanical property of polypropylene and processing characteristics in reaction process; 3) directly copolymerization: by propylene monomer and the monomer direct copolymerization under the effect of catalyzer with functional group, the multipolymer of preparation containing specific functional groups.Although direct copolymerization method introduces specific functional groups method the most fast in polypropylene, but the functional poly propylene that degree of isotacticity is very high can not be obtained, and very easily form stable complex compound and inactivation with N, O atom on polar monomer due to conventional Ziegler-Natta catalyst and metallocene catalyst, greatly limit its suitability for industrialized production; 4) physical blending or surface-coated: these two kinds of methods are widely used in polypropylene modification because of advantages such as production cost are low, simple to operate, flexible and changeable.But isotatic polypropylene has high regularity and crystallizing power, this makes it and other polymkeric substance, or even the consistency of its homologue (as syndiotactic polypropylene, Atactic Polypropelene) is all very poor.When therefore modification being carried out to isotatic polypropylene by the method for physical blending or surface-coated, often need to use segmented copolymer containing isotatic polypropylene segment as compatilizer, obviously could improve the consistency of polypropylene and polar polymer.
Therefore, developing a kind of simple, synthetic method of being easy to industrialized terminal hydroxy group isotatic polypropylene, is very urgent.
Shiono etc. (Makromol. Chem. Rapid Commun. 1990,11:169) use TiCl
3/ Al (CH
2cH
3)
2cl catalyst system, take zinc ethyl as chain-transfer agent, first carries out propylene polymerization, passes into dry oxygen, be oxidized and acidolysis the end of polymerisate after polymerization terminates.Polymerisate ethanol is carried out extracting by them, divide into soluble part and soluble part.
13the analytical results of C-NMR shows, ethanol-soluble fraction is Atactic Polypropelene, and the mass ratio in polymerisate is lower than 25%, and its end has 70% for hydroxy-end capped; And the soluble part of ethanol is isotatic polypropylene, its end group is not hydroxyl, so they do not make clear to what group, does not after this see the report of follow-up work.Chinese invention patent (CN1781957A) metallocene/methylaluminoxane (MAO) catalyzing propone polymerization, after polymerization terminates, pass into dry air or oxygen, then the aqueous solution adding hydrogen peroxide and alkaline hydrated oxide processes, and has prepared the isotatic polypropylene that one end is hydroxyl.In this catalyst system, MAO consumption is very large, causes production cost very high, limits its popularization to a certain extent.In addition, polypropylene molecule amount prepared by the method is high, is unfavorable for utilizing terminal hydroxy group to carry out follow-up reaction.At present, the Ziegler-Natta catalyst of the main still load of the catalyzer of industrial production isotatic polypropylene.Therefore, it will be more competitive for preparing for Primary Catalysts the isotatic polypropylene that one end is hydroxyl with the Ziegler-Natta catalyst of load, more be conducive to reducing production cost, realize suitability for industrialized production.In addition, prepare by the method for adding chain-transfer agent the isotatic polypropylene that one end is hydroxyl, can regulate and control polyacrylic molecular weight, by molecular weight control in more rational scope, thus improve the efficiency of subsequent reactions.
Summary of the invention
The problem to be solved in the present invention is, overcomes deficiency of the prior art, provides isotatic polypropylene of a kind of terminal hydroxy group functionalization and preparation method thereof.
The present invention is with efficient TiCl
4/ MgCl
2for Primary Catalysts, cheap aluminum alkyls is promotor, chooses the industrial chain-transfer agent that is easy to get and external electron donor, carries out propylene polymerization.
The isotatic polypropylene of terminal hydroxy group functionalization provided by the present invention, one end of its polymer chain is hydroxyl, and its general structure is as follows:
Wherein, the arbitrary integer between n=69 ~ 355.
Described polypropylene is isotactic polyprophlene, [mmmm]>=95%, and number-average molecular weight is 3 ~ 15 × 10
3mol/g, molecular weight distributing index is 3 ~ 10, terminal hydroxy group ending ratio>=0.7.
Present invention also offers a kind of preparation method of isotatic polypropylene of simple, feasible terminal hydroxy group functionalization, step is as follows:
(1) under the condition of anhydrous and oxygen-free, 50 mL organic solvents, aluminum alkyls, silicane external electron donor and metal alkylide class chain-transfer agent as promotor are joined in Schlenk bottle, finally adds 40mg Primary Catalysts TiCl
4/ MgCl
2, pass into the propylene that pressure is 0.1 ~ 1.1Mpa; Controlling polymerization temperature is 40 ~ 80 DEG C, and polymerization time is 0.5 ~ 3h;
In described promotor, in Al and Primary Catalysts, the mol ratio of Ti is 40 ~ 200: 1;
Described silicane external electron donor is any one (preferred Cyclohexyl Methyl Dimethoxysilane) in dimethyl bicyclopentyl silane, Cyclohexyl Methyl Dimethoxysilane, second, isobutyl dimethoxy silane or diisopropyl dimethoxy silane, and in external electron donor in Si and Primary Catalysts the mol ratio of Ti be 3 ~ 20: 1;
Described metal alkylide class chain-transfer agent is dimethyl germanium, dimethyl magnesium, zinc ethyl or trimethyl aluminium (preferred zinc ethyl), and the mol ratio between Ti in chain-transfer agent in metal and Primary Catalysts is 3 ~ 150: 1;
(2) by the dioxygen oxidation that the polymerisate in step (1) is dry, oxidizing temperature is 80 ~ 120 DEG C;
(3) aqueous hydrochloric acid of the product 5mL 1mol/L in step (2) is carried out cancellation, make catalyst deactivation, after stirring 5 min, leave standstill separatory with separating funnel, in removing, the clear liquid of middle level;
(4) solvent in removing step (3) in solid product, then use distilled water and the drying of organic solvent repetitive scrubbing final vacuum, obtain the isotatic polypropylene that one end is hydroxyl.
In the present invention, described organic solvent is the one in toluene, dimethylbenzene, normal heptane, octane or sherwood oil, preferred toluene.
In the present invention, described metal alkylide class promotor is the one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, preferred triethyl aluminum.
Preferably, in described external electron donor, in Si and Primary Catalysts, the mol ratio of Ti is 5 ~ 10: 1.
Isotatic polypropylene of terminal hydroxy group functionalization of the present invention and preparation method thereof has following feature:
(1) feature of the isotatic polypropylene of terminal hydroxy group functionalization is that polypropylene is the polypropylene of high isotactic, and one end of chain is hydroxyl.
(2) Primary Catalysts used is TiCl
4/ MgCl
2catalyzer, promotor is cheap aluminum alkyls, and Al:Ti is than low.
(3) preparation method of the isotatic polypropylene of terminal hydroxy group functionalization: first propylene gas is polymerized under anhydrous and oxygen-free condition, then directly pass into dry oxygen to carry out being oxidized, being hydrolyzed the isotatic polypropylene that just can obtain terminal hydroxy group functionalization, preparation method is simple, easy.
Compared with prior art, beneficial effect of the present invention is:
1) chain-transfer agent used, without the need to special synthesis, can add together with Primary Catalysts, and can not reduce the polymerization activity of Primary Catalysts;
2) Primary Catalysts is industrial conventional TiCl
4/ MgCl
2catalyzer is not metallocene, is easy to realize industrialization;
3) can directly after polymerization terminate, pass into dry oxygen can generate terminal hydroxy group by raised temperature, simple to operate, easy;
4) the hydroxy-end capped rate of isotatic polypropylene middle-end of the terminal hydroxy group functionalization prepared by the present invention is high;
5) the isotatic polypropylene molecular chain of the terminal hydroxy group functionalization prepared has very high structural regularity;
6) can 3 ~ 15 × 10
3regulate and control polyacrylic number-average molecular weight within the scope of mol/g, the polypropylene of gained at maintenance isotatic polypropylene self character simultaneously, can ensure again the hyperergy of terminal hydroxyl, be conducive to the carrying out of follow-up functionization reaction.
7) the present invention does not need to change greatly existing propylene polymerization device, just can be used for the isotatic polypropylene preparing terminal hydroxy group functionalization.
Accompanying drawing explanation
Fig. 1 is typical infrared spectrum in embodiment of the present invention 1-5;
Fig. 2 is typical in the embodiment of the present invention 3
1h NMR schemes.
Embodiment
Embodiment 1
Catalyzer: TiCl
4/ MgCl
2
Promotor: triethyl aluminum
Chain-transfer agent: zinc ethyl
External electron donor: Cyclohexyl Methyl Dimethoxysilane
Solvent: toluene
Under the condition of anhydrous and oxygen-free, by 50mL solvent, promotor triethyl aluminum (Al:Ti=60:1, mol ratio), external electron donor Cyclohexyl Methyl Dimethoxysilane (Si:Ti=5:1, mol ratio) and chain-transfer agent zinc ethyl (Zn:Ti=3:1, mol ratio) join in Schlenk bottle, finally add 40 mg Primary Catalystss, pass into the propylene that pressure is 0.1 MPa, polymerization temperature is 60 DEG C, and polymerization time is 0.5h.Pass into dry oxygen after polymerization terminates to be oxidized, at 100 DEG C, react 0.5h.Then add 5mL1mol/L aqueous hydrochloric acid and carry out cancellation, make catalyst deactivation.Separatory is left standstill with separating funnel, in removing, the clear liquid of middle level after stirring 5 min.Solvent in removing solid product, then use distilled water and the drying of organic solvent repetitive scrubbing final vacuum, obtain the isotatic polypropylene that 2.48g one end is hydroxyl.The number-average molecular weight of polymkeric substance is 11.2 × 10
3mol/g, molecular weight distributing index is 8.2, and fusing point is 158.8 DEG C, terminal hydroxy group ending ratio 0.71.
Embodiment 2
Other experiment condition is with embodiment 1, Zn:Ti=5(mol ratio).Obtain the isotatic polypropylene that 3.16g one end is hydroxyl.The number-average molecular weight of polymkeric substance is 16.3 × 10
3mol/g, molecular weight distributing index is 7.7, and fusing point is 159.6 DEG C, terminal hydroxy group ending ratio 0.73.
Embodiment 3
Other experiment condition is with embodiment 1, Zn:Ti=10(mol ratio).Obtaining 2.15 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 8.2 × 10
3mol/g, molecular weight distributing index is 7.0, and fusing point is 157.5 DEG C, terminal hydroxy group ending ratio 0.75.
Embodiment 4
Other experiment condition is with embodiment 1, Zn:Ti=15(mol ratio).Obtaining 2.15 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 5.9 × 10
3mol/g, molecular weight distribution is 7.0, and fusing point is 157.5 DEG C, terminal hydroxy group ending ratio 0.74.
Embodiment 5
Other experiment condition is with embodiment 1, Zn:Ti=20(mol ratio).Obtaining 1.76 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 5.7 × 10
3mol/g, molecular weight distributing index is 3.4, and fusing point is 157.6 DEG C, terminal hydroxy group ending ratio 0.77.
Embodiment 6
Other experiment condition is with embodiment 1, Zn:Ti=30(mol ratio).Obtaining 3.55 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 4.8 × 10
3mol/g, molecular weight distributing index is 8.1, and fusing point is 156.3 DEG C, terminal hydroxy group ending ratio 0.77.
Embodiment 7
Other experiment condition is with embodiment 1, Zn:Ti=40(mol ratio).Obtaining 2.23 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 3.7 × 10
3mol/g, molecular weight distributing index is 6.6, and fusing point is 157.3 DEG C, terminal hydroxy group ending ratio 0.81.
Embodiment 8
Catalyzer: TiCl
4/ MgCl
2
Promotor: trimethyl aluminium
Chain-transfer agent: dimethyl germanium
External electron donor: second, isobutyl dimethoxy silane
Solvent: dimethylbenzene
Under the condition of anhydrous and oxygen-free, by 50 mL solvents, promotor trimethyl aluminium (Al:Ti=40:1, mol ratio), external electron donor second, isobutyl dimethoxy silane (Si:Ti=10:1, mol ratio) and chain-transfer agent dimethyl germanium (Ga:Ti=30:1, mol ratio) join in Schlenk bottle, finally add 40 mg Primary Catalystss, pass into the propylene that pressure is 0.1MPa, polymerization temperature is 60 DEG C, and polymerization time is 1h.Pass into dry oxygen after polymerization terminates to be oxidized, at 120 DEG C, react 0.5 h.Then add 5 mL 1 mol/L aqueous hydrochloric acids and carry out cancellation, make catalyst deactivation.Separatory is left standstill with separating funnel, in removing, the clear liquid of middle level after stirring 5 min.Solvent in removing solid product, then use distilled water and the drying of organic solvent repetitive scrubbing final vacuum, obtaining 2.58 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 6.7 × 10
3mol/g, molecular weight distributing index is 6.6, and fusing point is 162.7 DEG C, terminal hydroxy group ending ratio 0.74.
Embodiment 9
Other experiment condition is with embodiment 8, and chain-transfer agent is dimethyl magnesium (Mg:Ti=30:1, mol ratio).Obtaining 3.13 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 3.1 × 10
3mol/g, molecular weight distributing index is 8.0, and fusing point is 160.1 DEG C, terminal hydroxy group ending ratio 0.80.
Embodiment 10
Other experiment condition is with embodiment 8, and chain-transfer agent is trimethyl aluminium (Al:Ti=30:1, mol ratio).Obtaining 2.56 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 3.0 × 10
3mol/g, molecular weight distributing index is 3.6, and fusing point is 158.2 DEG C, terminal hydroxy group ending ratio 0.78.
Embodiment 11
Other experiment condition is with embodiment 8, and promotor is triisobutyl aluminium (Al:Ti=30:1, mol ratio).Obtaining 1.99 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 9.8 × 10
3mol/g, molecular weight distributing index is 6.8, and fusing point is 156.4 DEG C, terminal hydroxy group ending ratio 0.75.
Embodiment 12
Catalyzer: TiCl
4/ MgCl
2
Promotor: triisobutyl aluminium
Chain-transfer agent: dimethyl magnesium
External electron donor: second, isobutyl dimethoxy silane
Solvent: normal heptane
Under the condition of anhydrous and oxygen-free, by 50 mL solvents, promotor triisobutyl aluminium (Al:Ti=200:1, mol ratio), external electron donor second, isobutyl dimethoxy silane (Si:Ti=10:1, mol ratio) and chain-transfer agent dimethyl magnesium (Mg:Ti=30:1, mol ratio) join in Schlenk bottle, finally add 40 mg Primary Catalystss, pass into the propylene that pressure is 0.6 MPa, polymerization temperature is 60 DEG C, and polymerization time is 1 h.Pass into dry oxygen after polymerization terminates to be oxidized, at 120 DEG C, react 0.5 h.Then add 5 mL 1 mol/L aqueous hydrochloric acids and carry out cancellation, make catalyst deactivation.Separatory is left standstill with separating funnel, in removing, the clear liquid of middle level after stirring 5 min.Solvent in removing solid product, then use distilled water and the drying of organic solvent repetitive scrubbing final vacuum, obtaining 6.35 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 12.8 × 10
3mol/g, molecular weight distributing index is 8.8, and fusing point is 157.7 DEG C, terminal hydroxy group ending ratio 0.82.
Embodiment 13
Other experiment condition is with embodiment 12, and external electron donor is Cyclohexyl Methyl Dimethoxysilane.Obtaining 6.21 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 5.5 × 10
3mol/g, molecular weight distributing index is 4.4, and fusing point is 154.2 DEG C, terminal hydroxy group ending ratio 0.70.
Embodiment 14
Other experiment condition is with embodiment 12, and external electron donor is dimethyl bicyclopentyl silane.Obtaining 6.17 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 4.6 × 10
3mol/g, molecular weight distributing index is 5.7, and fusing point is 164.4 DEG C, terminal hydroxy group ending ratio 0.74.
Embodiment 15
Other experiment condition is with embodiment 12, and external electron donor is diisopropyl dimethoxy silane.Obtaining 6.35 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 5.9 × 10
3mol/g, molecular weight distributing index is 8.8, and fusing point is 161.3 DEG C, terminal hydroxy group ending ratio 0.71.
Embodiment 16
Catalyzer: TiCl
4/ MgCl
2
Promotor: triethyl aluminum
Chain-transfer agent: trimethyl aluminium
External electron donor: Cyclohexyl Methyl Dimethoxysilane
Solvent: octane
Under the condition of anhydrous and oxygen-free, by 50 mL solvents, promotor triethyl aluminum (Al:Ti=100:1, mol ratio), external electron donor Cyclohexyl Methyl Dimethoxysilane (Si:Ti=10:1, mol ratio) and chain-transfer agent trimethyl aluminium (Al:Ti=150:1, mol ratio) join in Schlenk bottle, finally add 40 mg Primary Catalystss, pass into the propylene that pressure is 1.1 MPa, polymerization temperature is 60 DEG C, and polymerization time is 3 h.Pass into dry oxygen after polymerization terminates to be oxidized, at 120 DEG C, react 0.5 h.Then add 5 mL 1 mol/L aqueous hydrochloric acids and carry out cancellation, make catalyst deactivation.Separatory is left standstill with separating funnel, in removing, the clear liquid of middle level after stirring 5 min.Solvent in removing solid product, then use distilled water and the drying of organic solvent repetitive scrubbing final vacuum, obtaining 12.04 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 15.0 × 10
3mol/g, molecular weight distributing index is 4.5, and fusing point is 159.7 DEG C, terminal hydroxy group ending ratio 0.78.
Embodiment 17
Other experiment condition is with embodiment 16, and propylene pressure is 0.5MPa, the Al:Ti=100(mol ratio in chain-transfer agent trimethyl aluminium).Obtaining 5.01 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 6.8 × 10
3mol/g, molecular weight distributing index is 6.8, and fusing point is 158.4 DEG C, terminal hydroxy group ending ratio 0.79.
Embodiment 18
Other experiment condition is with embodiment 16, and propylene pressure is 1.1 MPa, the Al:Ti=150(mol ratio in chain-transfer agent trimethyl aluminium).Obtaining 13.18 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 10.2 × 10
3mol/g, molecular weight distributing index is 7.5, and fusing point is 163.2 DEG C, terminal hydroxy group ending ratio 0.82.
Embodiment 19
Other experiment condition is with embodiment 16, and polymerization temperature is 80 DEG C.Obtaining 1.97 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 4.8 × 10
3mol/g, molecular weight distributing index is 7.8, and fusing point is 161.2 DEG C, terminal hydroxy group ending ratio 0.77.
Embodiment 20
Other experiment condition is with embodiment 16, and polymerization temperature is 40 DEG C.Obtaining 2.87 g one end is the isotatic polypropylene of hydroxyl.The number-average molecular weight of polymkeric substance is 5.7 × 10
3mol/g, molecular weight distributing index is 4.8, and fusing point is 158.1 DEG C, terminal hydroxy group ending ratio 0.72.
The present invention adopts the method for end-functionalization, first hydroxyl is introduced at the end of isotatic polypropylene, be reactive functional groups with hydroxyl again, introduce other polarity segment or functional group, possessed following advantage: the problem that 1) there is not catalyst deactivation in direct copolymerization method; 2) do not changing under polypropylene physicals (fusing point, degree of crystallinity, melting index etc.) prerequisite, realize the functionalization of isotatic polypropylene, the isotatic polypropylene of assurance function and isotatic polypropylene matrix have good consistency; 3) can from the polypropylene of end group functional, end group is transformed into the group that can cause controllable free-radical polymerisation or anionoid polymerization, thus prepare various types of segmented copolymer, as the surface-modifying agent of isotatic polypropylene or the compatilizer with other polar polymers.This, by greatly expanding the range of application of isotatic polypropylene, has broad application prospects.
Claims (1)
1. a preparation method for the isotatic polypropylene of terminal hydroxy group functionalization, is characterized in that, comprises the following steps:
(1) under the condition of anhydrous and oxygen-free, 50mL organic solvent, aluminum alkyls, silicane external electron donor and metal alkylide class chain-transfer agent as promotor are joined in Schlenk bottle, finally adds 40mg Primary Catalysts TiCl
4/ MgCl
2, pass into the propylene that pressure is 0.1 ~ 1.1Mpa; Controlling polymerization temperature is 40 ~ 80 DEG C, and polymerization time is 0.5 ~ 3h;
In described promotor, in Al and Primary Catalysts, the mol ratio of Ti is 40 ~ 200: 1;
Described silicane external electron donor is any one in dimethyl bicyclopentyl silane, Cyclohexyl Methyl Dimethoxysilane, second, isobutyl dimethoxy silane or diisopropyl dimethoxy silane, and in external electron donor in Si and Primary Catalysts the mol ratio of Ti be 3 ~ 20: 1;
Described metal alkylide class chain-transfer agent is dimethyl germanium, dimethyl magnesium, zinc ethyl or trimethyl aluminium, and the mol ratio between Ti in chain-transfer agent in metal and Primary Catalysts is 3 ~ 150: 1;
(2) by the dioxygen oxidation that the polymerisate in step (1) is dry, oxidizing temperature is 80 ~ 120 DEG C;
(3) aqueous hydrochloric acid of the product 5mL 1mol/L in step (2) is carried out cancellation, make catalyst deactivation, stir after 5min and leave standstill separatory with separating funnel, in removing, the clear liquid of middle level;
(4) solvent in removing step (3) in solid product, then use distilled water and the drying of organic solvent repetitive scrubbing final vacuum, obtain the isotatic polypropylene that one end is hydroxyl;
Described organic solvent is the one in toluene, dimethylbenzene, normal heptane, octane or sherwood oil;
Described promotor is the one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium.
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| CN105694055A (en) * | 2016-02-23 | 2016-06-22 | 浙江大学 | Isotactic polypropylene-b-polytetrafluoroethylene double-segment polymer and method for preparing same |
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| CN109233106B (en) * | 2018-09-25 | 2021-06-29 | 宁波瑞成包装材料有限公司 | Production method of low-cost high-barrier polypropylene film |
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| CN109280270B (en) * | 2018-09-25 | 2021-06-29 | 宁波瑞成包装材料有限公司 | Production method of high-temperature-resistant high-barrier polypropylene film |
| CN109233105B (en) * | 2018-09-25 | 2021-06-29 | 宁波瑞成包装材料有限公司 | Production method of stretch-resistant high-barrier polypropylene film |
| CN109485754B (en) * | 2018-11-21 | 2021-01-12 | 江苏中煦聚烯烃研究院有限公司 | Polypropylene containing hydroxyl and preparation method thereof |
| CN115612201B (en) * | 2022-06-06 | 2023-12-26 | 湖南美莱珀科技发展有限公司 | Flame-retardant polypropylene material with improved mechanical properties and production method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
| CN1781957A (en) * | 2004-11-29 | 2006-06-07 | 中国科学院化学研究所 | Hydroxy terminated polypropylene and its preparing method |
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|---|---|---|---|---|
| CN101225130A (en) * | 2007-12-05 | 2008-07-23 | 浙江大学 | Stereo-tacticity regulator used for propylene polymerization and uses thereof |
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| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
| CN1781957A (en) * | 2004-11-29 | 2006-06-07 | 中国科学院化学研究所 | Hydroxy terminated polypropylene and its preparing method |
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